A brief summary of thermodynamic properties of various ternary systems investigated by EMF and...
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A brief summary of thermodynamic properties of
various ternary systems investigated by EMF and
Calorimetric method
Sabine Knott and Adolf MikulaInstitute of Inorganic Chemistry-Materials Chemistry
Währingerstr. 42, A-1090 Vienna, Austria
Investigated Systems
EMF and Calorimetry
EMF
Calorimetry
AlSnZnAgSnZnCuSnZnBiInZn
BiSnAgBiSnCuInZnPdSnZn
CuInBiInSnCuInSn
AgAuSn AuCuSnAgAlSn 14 binary and ternary systems
EMF Measurements
Partial Quantities__ΔG = -zFE
= exp (ΔG/RT)
Gibbs Helmholtz Equation•
__ΔH = -z(∂E/∂T)F-zFE__ΔS = z(∂E/∂T)F
STHG
T [K]
850 900 950 1000 1050 1100
EM
F [m
V]
0,0
0,5
1,0
1,5
2,0
2,5
3,0
3,5
4,0
4,5
5,0
FTE
zS
zFEFTE
zH
EMF Apparatus
Electrodes: Mo or W wire
Quartz container
Valve for evacuation
sample
Liquid electrolyte LiCl/KCl/XCly (X= Al, Zn, Sn), (y=2,3)
EMF Measurements
Integral Quantities
Gibbs-Duhem Equation x
ΔGEM=(1-xx)[ΔGE
M,x=0+∫dxx]y/z 0
__ΔGE
x = RT lnx
= lnx / (1-xx)2
21 )( x
x
x
H
Drop Calorimetry
SetaramMicrocalorimeter
200-1000°C, automatic sample device (max. 30 drops/measurement) controller/data aquisition with LabView, evaluation with HiQCalibration with NIST-sapphire
Calorimetry
HSignal = ni. (Hsample,FT-Hsample,DT) + HReaction
__
ΔHi = (HSignal/ni) – (Hsample,FT-Hsample,DT)
ΔHMIX =Hbin + ΣHReaction /(n+Σni)
Redlich Kister Muggianu Polynom
CCBABCBAACBACBAji ij
ijijimix xMxMxMxxxxxLxxH )(::
)(::
)(::
)(: )( 210
Isoenthalpy lines of the ternary Cu-In-Sn systemat 1073 K
Lν i,j binary interaction parameter
M ternary interaction parameter
Pd─Sn─Zn
Sn0,0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 0,9 1,0
Zn
0,0
0,1
0,2
0,3
0,4
0,5
0,6
0,7
0,8
0,9
1,0
Pd
0,0
0,1
0,2
0,3
0,4
0,5
0,6
0,7
0,8
0,9
1,0
Bi─In─Zn
In0,0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 0,9 1,0
Zn
0,0
0,1
0,2
0,3
0,4
0,5
0,6
0,7
0,8
0,9
1,0
Bi
0,0
0,1
0,2
0,3
0,4
0,5
0,6
0,7
0,8
0,9
1,0
Calorimetry, 500°C EMF, 600°C
Bi─In─Zn
Bi:In=1:1
xZn
0,0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 0,9 1,0
H (
J/m
ol)
-3000
-2000
-1000
0
1000
2000
3000
4000
5000
EMFCalorimetry
Enthalpy of mixing measured by EMF and Calorimetry
Y Djaballah, L Bennour, F Bouharkat and A Belgacem-BouzidaModelling Simul. Mater. Sci. Eng. 13 (2005) 361–369
BiInZn
at.%Zn
0 20 40 60 80 100
EM
K (
mV
)0
20
40
60
80
BiIn21BiIn21 (600°C)
Calorimetric measurementEMF measurement
Bi─In─Zn
Y Djaballah, L Bennour, F Bouharkat and A Belgacem-BouzidaModelling Simul. Mater. Sci. Eng. 13 (2005) 361–369
Ternary AgAuSn System
• Verschiedene Modelle:
• Extrapolationsmodelle nach Toop, Muggianu und Kohler
• Chou Modell
0.0 0.2 0.4 0.6 0.8 1.0-14000
-12000
-10000
-8000
-6000
-4000
-2000
0
2000
4000HM, J/mol
xAu
section with Sn:Ag 1:1 1:9 3:7 7:3 9:1
Ag:Sn=1:1
xAu
0,0 0,1 0,2 0,3 0,4 0,5 0,6 H
(J/
mol
)
-12000
-10000
-8000
-6000
-4000
-2000
0
exp. 1023 KKohlerMuggianuToop
Dragana Živković, Dragan Manasijević, Živan Živković, J. of the University of Chemical Technology and Metallurgy, (2004) 39(1), 63-76
Z.Li, M.Dallegri, S.Knott, ccepted for publication in J. of Alloys and Compounds
Ag-Bi-Sn vertical cross section Ag:Bi = 1:1
Δ-heating curve-cooling curve
Calcs based on [01Oht]Calcs based on [94Kat]
Cu-In
xIn
0,0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 0,9 1,0
H [J
/mo
l]
-8000
-6000
-4000
-2000
0
Kang, 973 KHultgren, 1073 KItagaki, 1373 K
xIn
0,0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 0,9 1,0
H [
J/m
ol]
-8000
-6000
-4000
-2000
0
973 K1073 K1073 K1173 K1273 K
973K
1073K, 1373K
xIn
0,0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 0,9 1,0
H [J
/mo
l]
-8000
-6000
-4000
-2000
0
Kang, 973 KHultgren, 1073 KItagaki, 1373 K973 K1073 K1073 K1173 K1273 K
CuInSn
Phase Diagram at different temperaturesLiu et al., J. Electronic Materials, 30(9), 2001, 1093
Experimental Procedure: Calorimetric Measurements at 1073 K and 973 K
Comparison Cu-In-Sn Kalorimetrie vs. Knudsen
A. Popovic, L. Bencze,International Journal of Mass Spectrometry 255 (2006) 41–49
Wetting angles
Systems: CuInSn, 5 at.%Cu
AgCuSn
0
20
40
60
80
100
120
We
ttin
g A
ng
le (
°)
Sn-
0.5A
g4C
uS
n-2A
g1.5
Cu
Sn-
2Ag0
.5C
uS
n-2.
5Ag0
.9C
uS
n-3A
g4C
uS
n-3A
g0.5
Cu
Sn-
3.2A
g0.8
Cu
Sn-
3.4A
g0.9
Cu
Sn-
03.5
Ag2
Cu
Sn-
3.5A
g0.7
Cu
Sn-
3.6A
g1C
uS
n-3.
8Ag2
.3C
uS
n-3.
8Ag0
.7C
uS
n-3.
9Ag0
.6C
uS
n-4A
g1C
uS
n-4A
g0.5
Cu
Sn-
4.7A
g1.7
Cu
Alloy
Cu Substrate
Ni Substrate
17 different alloysCopper and Nickel substrateCollophonium flux
Acknowledgements
• Dr. Zuoan Li
• FWF P16491–N11
• FWF P19469–N19
• COST 531
Thank you for your attention